Nitrothiophene insecticidal composition and process of using same



Patented Get. 12, 1954 NITROTHIOPHENE INSECTICIDAL COMPO- SITION ANDPROCESS OF USING SAME Joseph B. Dickey and Harry W. Ccover, J12,Rochester, N. Y., assignors to Eastman Kodak Company, Rochester, N. Y.,a corporation of New Jersey No Drawing. Application November 7, 1949,Serial No. 126,052

6 Claims. 1

This invention relates to compositions useful for insecticidal purposes.More specifically, the invention is concerned with insecticidalcompositions containing nitrothiophenes, together with a carriertherefor.

Compounds to be of value for insecticidal purposes should ordinarily belight-stable, compatible with light parafiinic mineral oils, free fromharmful effects to plants, free of a tendency to stain wcols, fabrics,etc., and be not offensive to human beings.

Many of the insecticides which are known at the present time areobjectionable on one or more of the above counts. Some Of theseinsecticides are short-lived in effectiveness. harmful to plants at theconcentrations and under the conditions used or else have some otherundesirable characteristic which interferes with the usefulness of thoseinsecticides in practical application.

One object of our invention is to provide insecticidal compositionswhich are highly toxic to insects but are of low toxicity to man andother warm-blooded animals. Another object of our invention is toprovide insecticidal compositions which are simple to use but are highlyeffective against various insects of a destructive nature, such as toplant life, food materials or the like. A further object of ourinvention is to provide compositions which are effective both as regardsinsects and as regards parasitic organisms which are ordinarilyclassified as fungi. A still further object of our invention is toprovide nitrothiophenes in a form which is highly useful for combatingharmful insect life. Other objects of our invention will appear herein.

We have found that the nitrothiophenes are highly effective ninsecticidal compositions for use in combating the most commonly knownforms of destructive insect life. The compounds which we have found tobe of value for this purpose are those having the following generalformula:

wherein X is selected from hydrogen, halogen, all'yl, aryl, carboxy,sulfonyl, CPI-=0 and ketones.

For example, a nitro group may occupy one or two of the availablepositions on the ring and- Carboxy and its derivatives, sulfonyl and itsde- Others are H rivatives, CH=O and its derivatives (oximes, hydrazonesand semi-caroazides), ketones and its derivatives. Compounds of the typewhich are useful in my invention are described in a survey of theliterature on these nitro compounds. See Steinkopf, Die Chemie desThiophenes; J. W. Edwards, Ann Arbor, Michigan; and Avery A. Morton TheChemistry of Heterocyclic Compounds, chapter 3, McGraw-Hill, New York.Also, some of these compounds are found in other literature references.

Compounds which are useful in our invention and which are described onpages 58 and 84 of Steinkopf are:

2- and B-nitrothiophene 2,4-dinitrothi0phene 2,5-dinitrothiophenei-nitrothiophene-2-carboxylic acid 2,5-dibromo-3-nitrothi0phene 3,5dinitro 4: methylthiophene 2 carboxylic ester 5 nitro 4 methylthiophene2 carboxylic ester 4,5-dichloro-2-nitrothiophene3,4,5-trich1oro-Z-nitrothiophene 2,5-dich1oro-3,4-dinitrothiophene and2,4-dibromo-3,5dinitrothiophene Other compounds of interest and theliterature references where their preparation is referred to is asfollows:

2,3 dichloro 5 nitrothiophene and 2 bromo- S-nitrothiophene-Ann. 532,250 (1937) 3,4 dibromo 2,5 dinitrothiophene-Ann. 512,

2-bromo-5-nitrothiophene 3 nitro 2,4,5 trichlorothiophene-Ann. 532,

250 new The disclosure in the Annalen in vol. 512, page 136, and vol.532, page 250, is to be considered as part of the present disclosure ofhalogenated nitrothiophenes useful in the compositions of thisinvention.

The insecticidal value of the nitrothiophenes is shown by various testscarried out by contacting insects with this compound. For instance, bypreparing a dust of a nitrothiophene and an inert carrier, such aspyrophyllite, and after placing fruit flies in a bottle, sprinkling withthe dust and observing the flies at intervals, it may be seen that 100%kill of those fruit flies is obtained in a short time. For instance,with 2,4-dinitrothiophene in such a test using a proportion of one partof the nitrothio phone to 100 parts of carrier a 100% kill was obtainedwithin one-half hour. With 2,5-dicliloro-3,4-dinitrothiophene in thesame type of test a complete kill was obtained within two hours. Intests with the nitrothiophenes in various concentrations it was foundthat the efiectiveness of dusts ranging in concentration from one partof nitrothiophene to parts of carrier to one part of a nitrothiophene to1000 parts of carrier substantially the same degree of kill was obtainedwhile with dusts in which greater dilutions were used, the eilectiveneswas not as great. For instance, using one part of a nitrothiophene in2000 parts of carrier, the kill in onehalf hour was slightly overone-half that obtained with a concentration of one part in 1000 parts ofcarrier. It was also found that the nitrothiophene in the form of aspray was highly effective for killing insects. It was also determinedthat the nitrothiophenes are effective even after standing forconsiderable periods of time. For instance, a nitrothiophene was placedin a Petri dish and was allowed to stand exposed to the air fortwenty-four hours and in another case for thirteen days beforedetermining efiec- .tiveness. The percent of Tribolium which wasparalyzed in eighteen hours after contacting with the nitrothiophenewhich had stood for twenty-hours was found to be 93%. In the case of thematerial which had stood for thirteen days similar results wereobtained, namely, 93% paralysis of Triboliuzn when contacted with thenitrothiophene for eighteen hours. The insecticidal compositions inaccordance with my invention are effective against various insecticidalpests, such as houseflies, silverfish, bean beetles, flea beetles,cucumber beetles, aphids, red spiders and other mites, thrips, etc.

We have also found that in the case of the halogenated nitrothiophencsthat good fungicidal properties are also displayed thereby. Forinstance, the efiectiveness of 2,5-dichloro-3A- dinitrothiophene inconcentrations of 1:400 1:800 and 111600 was determined in the case bothof Glomerella and Alternaria. In these tests complete growth is rated100 and no growth is rated 0. The following table gives the results ofthose tests compared with a check in which no nitrothiophene was used:

The proportion of the nitrothiophenes to be employed in insecticidalcompositions in accordance with our invention may vary over a widerange. For instance, insects having little or no protective covering arereadily susceptible to the efiect of these materials and thus, even aslittle as 0.5% thereof would be effective. Ordinarily, however, a higherpercentage of the nitrothiophene is desirable being most useful in theproportion of 140% in the composition. If desired, other insecticidalmaterials may be used as an additive to or to displace part of thenitrothiophone which is present in the insecticidal composition. Forinstance, insecticides, such as pyrethrum, rotenone, nicotine, calciumor lead arsenate, p-dichlorobenzene, or the like, may be incorporated inthe compositions in accordance with our inventions. If desired, mixturesof the nitrcthiophenes may be employed. In some cases it may bedesirable to also include fungicidal materials, such as lime-sulfur,sulfur, Bordeaux mixture, yellow copper oxide, mercury compounds, or thelike. Also, it may be desired to incorporate synergists in insecticidalcompositions in accordance with our invention to enhance theeffectiveness of those compositions. Some compounds which do notthemselves exhibit insecticidal properties but which increase theeiiectiveness of the nitrothiophenes are piperonyl butoxide, piperonylpropoxide, and piperonyl butyl carbitol oxide. A small proportional ofthe synergist may be incorporated in the composition, but any proportionfrom 0.5% up to 5% of that material may be employed to good efiect.

We have found that petroleum distillates are particularly effective assolvents in preparing nitrothiophene insecticidal compositions, such aspetroluem hydrocarbons having a boiling range of -150 C. Some of thepetroleum distillates which are useful in this connection are kerosene,ligroin, naphtha, and the like. For dusting compositions we have foundpyrophyllite to be of advantage for the carrier for the nitrothiopheneto be used in the insecticidal compositon.

The following examples illustrate compositions in accordance with ourinvention which are particularly efiective for insecticidal purposes:

Example 1.-The following composition is particularly effective for useas aerosols in which a propelling liquid is present:

. Per cent 2,4-olinitrothiophene 5 Refined petroleum distillate 12-15Per cent 2,4-dinitrothiophene 2 Pyrethrin extract 0.2 Piperonyl butoxide1 Petroleum distillate 12 Inert propellant 84.8

Example 3.-Instead of using a propellant a solution of nitrothiophene ina petroleum distillate is emulsified in water by means of an emulsifyingagent such as whale oil soap, ordinary soap, sodium lauryl sulfate, orsome other wetting agent. This aqueous emulsion is useful in the form ofa spray for application to areas where undesirable insect life is found.

Example 4.-A particularly effective insecticidal dusting compound isobtained by incorporating 540% of ZA-dinitrothiophene or some othernitrothiophene listed above in -95% of pyrophyllite in finely dividedform.

Example 5.-500 parts of pyrophyllite was impregnated with a solution of15 parts of 2,5-dichloro-2,3-dinitrothiophene in 275 parts of ethanol. Apaste was formed which was dried and ground to a powder. This powder wasfound to be useful for both insecticide and fungici e purposes.

Example 6.-'Ien parts of 2-chloro-5-bromo- BA-dinitrothiophene and 1part of pyrethrum extract were dissolved in 1000 parts of kerosene. Thesolution was sprayed onto seeds, plants,

cloth and the like. Good protection against insects and fungi wasobtained.

ExampZe7.Ten parts of 3,4-dibromo-2,5-dinitrothiophene, 1 part ofpiperonyl butoxide and 1000 parts of difiuorodichloromethane were placedin a bomb. This composition when sprayed into the air was found to beefiective for insecticidal purposes, achieving a substantially completekill in a short time.

Example 8.One part of 2,5-dich1oro-3,4-dinitrothiophene, 1 part of2,5-dibromo-3,4dinitrothiophene and 1 part of 2,5 dichloro 3nitrothiophene were dissolved in 500 parts of kerosene with 2 parts ofDDT, 1 part of piperonyl butoxide, and 1 part of The composition formedwas found to be efiective for insecticidal purposes.

We claim:

1. An insecticidal composition comprising an insecticidal proportion of2,4-dinitrothiophene and a refined petroleum distillate.

2. An insecticidal composition comprising an insecticidal proportion of2,4-dinitrothiophene and finely divided pyrophyllite.

3. A method of killing insects which comprises contacting the insectswith 2,4-dinitrothiophene.

4. An insecticidal composition essentially consisting of a uniformdispersion of 05-10% of an active ingredient having the formula:

wherein X are substituents selected from the groups, and an inertinsecticidal adjuvant as a carrier for the active ingredient.

5. An insecticidal composition essentially consisting of a uniformdispersion of 05-10% of 2,4- dinitrothiophene as the active ingredientand an inert insecticidal adjuvant as a carrier for the activeingredient.

6. A method of killing insects which comprises contacting the insectwith a nitrothiophene having the formula:

XJ (|'IJX X0 CX s wherein X are substituents selected from the groupconsisting of N02 and H, at least one and not more than 2 of thosesubstituents being nitro groups.

References Cited in the file of this patent UNITED STATES PATENTS NumberName Date 2,600,126 Nolan et a1 June 10, 1952 2,651,579 Plump Sept. 8,1953 FOREIGN PATENTS Number Country Date 526,066 Great Britain Sept. 10,1940 Frear: A Catalogue of Insecticides and Fungicides, vol. II, 1948,Waltham, Mass, Chronica Botanica 00., pages 27-28.

May et al.: Mays Chemistry of Synthetic Drugs, Longmans Green 8; 00., N.Y., 4th ed., 1939, page 9.

J. Am. Pharm. Assn, August 1948, pp. 317-319.

Dann: Chemical Abstracts (1947), vol. 1, pp. 3090-2.

Johnson et a1.: J. Biol. Chem, 153, pp. 37-47 (1944).

4. AN INSECTICIDAL COMPOSITION ESSENTIALLY CONSISTING OF A UNIFORMDISPERSION OF 0.5-10% OF AN ACTIVE INGREDIENT HAVING THE FORMULA: